Interactions Among the Copper Species and Forms in Sea Water/Sediments and Copper Bioaccumulation in Oysters

Abstract

Earlier papers indicated that the first incident of green discoloration in oysters (Crassostrea gigas) and the mass mortality observed in 1986 along the Taiwan Erhjin Chi coastal area were caused by the higher contents of total copper and copper species (mainly bioavailable and free ion) in sea water. the copper in sea water would be sorbed by suspended matter and transferred to sediments, and the copper in the sediments would also be desorbed to sea water. Processes of copper adsorption and desorption are the major factors influencing the contents of total copper and copper species in sea water and sediments. in this study, the Erhjin Chi sediments were mixed with sea water by a shaker technique. When the mixture was shaken for one hour, analogous to tidal mixing in estuaries, only copper desorption from sediments was observed. If the shaking time is increased for more than 3 hours, the copper released from the sediments was resorbed to the remaining solid phases. the higher the contents of mud (91.71%) and total copper (701 mg kg^?1) in sediments, the higher the copper desorption rate (1.86 ppm hr^?1) and copper adsorption rate (0.50 ppm hr^?1) were observed. in sediments containing lower mud (0.80%) and lower copper (43.5 mg kg^?1), the copper desorption and adsorption rates were 0.83 ppm hr^?1 and 0.22 ppm hr^?1, respectively. the interactions among the total copper and copper species in sea water and sediments, chemical and ecological parameters, and copper bioaccumulation in oysters in the Erhjin Chi estuarine and coastal area are also discussed.     

Relationships Between Copper Species and Forms,Hydrographic and Biomass Parameters in the Taiwan Erhjin Chi Coastal Area

The first incident of green oysters (Crassostrea gigas) was reported in Taiwan in the Charting coastal area in January, 1986 and mortality was reported three months later. the cause of the greened oysters was identified as copper pollution. the copper content of the green oysters was extremely high - 2100 ppm, 2225 ppm, and 4400 ppm dry weight, in January, 1986, February 1987, and January 1989, respectively. in this paper we summarize the seasonal and regional distributions of copper species (complexed by inorganic and organic ligands, labile and non-labile, polar and non-polar) and forms (dissolved and particulate) and the hydrographic and biomass parameters (mainly particulate organic carbon, chloropyll -α, adenosine triphosphate and primary production) in sea water in the Erhjin Chi coastal area. in general, high concentrations of particulate material (0.24 to 724 ppb) and non-labile organic copper (0.03 to 21.5 ppb) were observed. Low values of polar organic copper (<0.02 to 16.5 ppb) indicated that non-polar organic complexes (0.3 to 20.4 ppb) from man-made organic pollutants were the major complexes in the area studied. On the basis of this data, the cause of greening and mortality in oysters is evaluated in relation to the bioavailable copper (sum of particulate and labile copper) and copper assimilative capacity (detoxicant). Finally, the correlations between the species and forms of copper, hydrographic and biomass parameters are also discussed.     

Species of Trace Metals, Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^-1, dry weight in fulvic acid and 820μg g^-1 in humic acid) and lead (821μg g^-1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Species distribution of arsenic in sediments after an unexpected emergent discharge of high-arsenic wastewater into a river

The unexpected emergent discharge of high-arsenic wastewater into water environments results in significantly increased levels of arsenic in water; however, the species distribution of arsenic in sediments has never been reported before for such cases. This study focuses on an As pollution accident in the Dasha River, and uses sequential extraction procedures with deionized water, 1?mol·L^-1 MgCl₂ at pH= 8, 1?mol·L^-1 NaH₂PO₄ at pH= 5, and 1?mol·L^-1 HCl to investigate four binding phases of arsenic (i.e., water soluble, ion-exchangeable, strongly-bound, and precipitates) in sediments at different layers in different cross-sections along the river. The average ratio of arsenite (As(III)) to arsenate (As(V)) was found to decrease from 0.74:1 in river water to 0.48:1 in sediment, owing to its higher affinity toward As(V) than As(III). The content of arsenic in the sediments was relatively low and the maximum content was observed to be 36.3?mg·kg^-1 for As(III) and 97.5?mg·kg^-1 for As(V). As(III) and As(V) showed different binding phases in sediments, and the average fractions of these four species were determined to be 0.09, 0.11, 0.17, and 0.63 for As(III) and 0.03, 0.14, 0.63, and 0.20 for As(V), respectively. For all the sediment samples, the content of arsenic showed no relationship with the characteristics of the sediments such as the particle diameter, the content of organic carbon, Fe, and Mn, although a negative correlation with particle diameter was observed for the sediments in the uppermost 2-cm layer. The unexpected emergent As incident results in the high content of total arsenic in the surface sediment, which may be potential secondary source to the elevated As levels in surface water.     

生物炭对土壤中阿特拉津吸附特征的影响

为探究生物炭对土壤中阿特拉津的吸附特征及影响因素,采用批处理实验研究了灭菌(T1)、5%秸秆生物炭+灭菌(T2)、未灭菌(T3)和5%秸秆生物炭+未灭菌(T4)条件下对土壤中阿特拉津吸附特征及土壤理化性质的影响.结果表明,在最初0—12 h内,不同处理下阿特拉津吸附量均随时间的延长而快速增加,而在12—96 h内增加较为缓慢并逐渐趋于平衡.在96 h时,T2和T4处理下阿特拉津最大吸附量分别达到46.22 mg·kg^-1和46.43 mg·kg^-1,而未添加生物炭的T1和T3处理则有所降低,分别为44.20 mg·kg^-1和43.09 mg·kg^-1.准二级动力学模型更好地拟合不同处理下土壤对阿特拉津吸附特征,T2和T4处理下吸附速率常数K分别为0.257 kg·mg^-1·h^-1和0.339 kg·mg^-1·h^-1,显著高于未添加生物炭处理的T1和T3处理(K分别为-0.083 kg·mg^-1·h^-1和-0.261 kg·mg^-1·h^-1).内扩散模型显示添加生物炭后,土壤对阿特拉津的吸附是一个由边界扩散、内部孔隙扩散等多因素控制的复杂化学过程.添加生物炭可显著提高土壤pH、有机碳、碱解氮、速效磷和速效钾含量,其中土壤有机碳含量与阿特拉津最大吸附量之间存在显著的正相关关系(P<0.05).由此可见,添加生物炭可以提高土壤对阿特拉津的固持能力,减少其淋溶迁移风险,从而达到修复阿特拉津污染土壤的目的.     

水中天然含氮有机物的形成、迁移转化及分布

天然含氮有机物是水环境中的重要组成部分,其在天然水体中的形态及分布对环境质量有显著影响.本文围绕水中天然含氮有机物在氮循环中的地位、迁移转化以及其在国内主要水域中的分布情况,对天然含氮有机物的研究现状进行了梳理.我国不同水域中溶解性含氮有机物(DON)浓度相差较大;其中水体中DON浓度一般在1.0 mg·L^-1以下;沉积物中DON浓度通常为几十至几百mg·kg^-1.水体DON以分子量<1 kDa的有机物为主,主要成分是尿素、氨基酸等物质.沉积物DON以分子量<1 kDa和>30 kDa的有机物为主,其中前者主要由芳构化程度较高的氨基酸等小分子有机物构成,后者以腐殖质类为主.水体中部分胺类物质本身具有一定毒性,游离氨基酸等DON还是卤乙腈、卤代酰胺、卤代硝基甲烷、卤化氰和亚硝胺等含氮消毒副产物的重要前体物.由于水体中许多含氮有机物具有生物可利用性,有机氮可能是引起水体富营养化的重要原因之一.     

Species of Trace Metals,Organic Residues and Humic Substances in Sediments From the Taiwan Erhjin River and Coastal Areas

Abstract

Total organic carbon, humic substances, and the species of trace metals (including Cu, Zn, Pb, Cd, Cr, Mn and Fe) in six and seven phases, such as bioexchangeable (P1), skeletal (carbonates, P2), easily reducible (Fe and Mn oxides, P3), moderately reducible (crystalline Mn oxides, P4), organic matters with sulphides (P5), and detritus with minerals (P6) as well as organic with humic substances (PB4) and organic residues (PB6), were analyzed in sediments from the Taiwan Erhjin coastal (including river and estuarine) area, where places we found the copper pollution. Results indicate that higher percentages of P1 and P2 for copper, zinc, lead, cadmium and manganese in samples collected in March and September of 1990 were much higher than those in P3-P6. High percentages of chromium and iron in samples respectively collected in March and September of 1990 were found in P6. for the seven phase analysis, higher percentages of copper species in PB4 and PB6 as well as iron species in PB7 were observed. On the other hand, purified humic acid with the high contents of manganese and iron in humic acid as well as purified fulvic acids were generally found at the upstream stations; and low values at coastal stations. However, extremely high copper (as high as 1750μg g^?1, dry weight in fulvic acid and 820μg g^?1 in humic acid) and lead (821μg g^?1 in humic acid) concentrations with relatively high manganese and iron concentrations were observed in humic substances from the station near the copper recycling area. Comparing the results obtained from the Antarctic Ocean sediments with those from the Taiwan Erhjin Chi coastal sediments, the human impacts on the latter are evaluated.     

Simultaneous quantification of several classes of antibiotics in water,sediments, and fish muscles by liquid chromatography–tandem mass spectrometry

Precise and sensitive methods for the simultaneous determination of different classes of antibiotics, including sulphonamides, fluoroquinolones, macrolides, tetracyclines, and trimethoprim in surface water, sediments, and fish muscles were developed. In water samples, drugs were extracted with solid-phase extraction (SPE) by passing 1000 mL of water through hydrophilic lipophilic balanced (HLB) SPE cartridges. Sediment samples were solvent-extracted, followed by tandem SPE (strong anion exchange (SAX) + HLB) clean-ups. Fish muscles were extracted by a mixture of acetonitrile and citric buffer (80:20, v/v) solution, and cleaned by SPE. Liquid chromatography–tandem mass spectrometry (LC-MS/MS) with multiple reaction monitoring (MRM) detection was employed to quantify all compounds. The recoveries for the antibiotics in the spiked water, sediment, and fish samples were 60.2%–95.8%, 48.1%–105.3%, and 59.8%–103.4%, respectively. The methods were applied to samples taken from Dianchi Lake, China. It showed that concentrations of the detected antibiotics ranged from limits of quantification (LOQ) to 713.6 ng·L^-1 (ofloxacin) in surface water and from less than LOQ to 344.8 μg·kg^-1 (sulphamethoxazole) in sediments. The number of detected antibiotics and the overall antibiotic concentrations were higher in the urban area than the rural area, indicating the probable role of livestock and human activities as important sources of antibiotic contamination. In fish muscles, the concentration of norfloxacin was the highest (up to 38.5 μg·kg^-1), but tetracyclines and macrolides were relatively low. Results showed that the methods were rapid and sensitive, and capable of determining several classes of antibiotics from each of the water, sediment, and fish matrices in a single run.     

The Freshwater Mussel Parreysia Favidens (Benson) As A Biological Indicator of Polonium - 210 in A Riverine System

The concentration of ²¹⁰Po, an alpha emitter from the natural uranium series was measured in the soft tissues (total), shell, and different organs - digestive glands, gills, mantle and foot - of the freshwater mussel, Parreysia favidens (Benson), collected from the river Kaveri, at Tiruchirapalli in South India. the analyses were made in three size groups based on shell length (Group 1: 2-4 cm; Group 2: 4-5 cm; Group 3: 5-6 cm). the soft tissues of the mussel accumulated higher concentrations of ²¹⁰Po (74.0-125.5 Bq kg^-1 fresh) than the shell (2.9-3.9 Bq kg^-1 fresh). Further, younger mussels (1 group) showed higher concentrations (125.5+2.0 Bq kg^-1 fresh) in total soft tissues than older ones (III Group) (74.0+1.6 Bq kg^-1 fresh); concentration factors were 1.59x 10⁵ in I group and 9.37 × 10⁴ in III group. the ²¹⁰Po was observed to be non-uniformly distributed among the internal organs, which maintained the following descending order with reference to ²¹⁰Po accumulation: digestive glands, ranging from 286.2+3.5 Bq kg^-1 fresh to 43+1.3 Bq kg^-1 fresh. the concentration of ²¹⁰Po in the mussels was distinctly higher than that in the grass, Echinochloa colonum (J. Koenig), and carp, Cirrhinus cirrhosa (Bloch), from the same river. These data indicate that younger mussels could be used as an excellent biological indicator of ²¹⁰Po and among soft tissues, digestive glands are preferable to other tissues to monitor the distribution of ²¹⁰Po in the riverine system.     

Contributions of adsorption,bioreduction and desorption to uranium immobilization by extracellular polymeric substances

● EPS immobilizes U(VI) via adsorption, bioreduction and desorption. ● This work provides a framework to quantify the three immobilization processes. ● The non-equilibrium adsorption of U follows pseudo-second-order kinetics. ● The equilibrium adsorption of U followed Langmuir and Freundlich isotherms. Hexavalent uranium (U(VI)) can be immobilized by various microbes. The role of extracellular polymeric substances (EPS) in U(VI) immobilization has not been quantified. This work provides a model framework to quantify the contributions of three processes involved in EPS-mediated U(VI) immobilization: adsorption, bioreduction and desorption. Loosely associated EPS was extracted from a pure bacterial strain, Klebsiella sp. J1, and then exposed to H₂ and O₂ (no bioreduction control) to immobilize U(VI) in batch experiments. U(VI) immobilization was faster when exposed to H₂ than O₂ and stabilized at 94% for H₂ and 85% for O₂, respectively. The non-equilibrium data from the H₂ experiments were best simulated by a kinetic model consisting of pseudo-second-order adsorption (k_a = 2.87 × 10⁻³ g EPS·(mg U)⁻¹·min⁻¹), first-order bioreduction (k_b = 0.112 min⁻¹) and first-order desorption (k_d = 7.00 × 10⁻³ min⁻¹) and fitted the experimental data with R² of 0.999. While adsorption was dominant in the first minute of the experiments with H₂, bioreduction was dominant from the second minute to the 50^th min. After 50 min, adsorption was negligible, and bioreduction was balanced by desorption. This work also provides the first set of equilibrium data for U(VI) adsorption by EPS alone. The equilibrium experiments with O₂ were well simulated by both the Langmuir isotherm and the Freundlich isotherm, suggesting multiple mechanisms involved in the interactions between U(VI) and EPS. The thermodynamic study indicated that the adsorption of U(VI) onto EPS was endothermic, spontaneous and favorable at higher temperatures.     

Zn和Cd胁迫作用对长梗白菜形态和生理性能的生态毒理影响

本文以不同Cd、Zn浓度胁迫下的长梗白菜为研究对象,采用盆栽实验,分析了Cd和Zn胁迫下长梗白菜形态参数(重量、长度、表面积、叶的分形维数)、生理性能的影响以及从土壤中提取Cd和Zn的能力.结果 表明,Cd、Zn胁迫对长梗白菜的生长具有"低促高抑"效应,且共同胁迫对生长的影响大于单一胁迫.在0.6 mg·kg-1 Cd...     

Bioaccumulation and elimination of copper in the rock oyster Crassostrea cucullata

The kinetics of copper bioaccumulation in the rock oyster Crassostrea cucullata Born showed that the initial rate of uptake was directly related to metal concentration in the medium. As the accumulation in the tissues increased, the oysters remained closed and the uptake rate fell. At the end of 7 weeks, the average copper concentrations in the tissue were 60.42 g g^-1 and 63.97 g g^-1 wet weight in the 0.01 and 0.05 ppm experimental groups, respectively. The net rate of uptake ranged from 1.76 to 1.97 g g^-1 week^-1 and the rate of copper loss, measured after transferring the oysters into natural sea water, was dependent on the original cooper concentration in the soft parts. The concentration of copper in the tissues declined by 37.38 and 36.56% in the 0.01 and 0.05 ppm experimental groups, respectively. Even after a 7 week period of depuration (self-purification) there was some residual copper left in the tissue. This indicates that accumulation occurs in the tissue more rapidly than cleansing can eliminate it.     

Radioactive Isotopes of Strontium, Caesium and Plutonium in Sediments of the Northern Adriatic Sea

Sediment samples of different strata (0-3 and 12-15 cm) were collected between 1990 and 1992 during seasonal cruises in the Northern Adriatic Sea. A complete mapping of the Sr-90, Cs-137, Pu-238 and Pu-239(240) concentrations was obtained for samples covering a wide area, stretching from the Gulf of Trieste towards the Ancona shoreline. Sr-90 concentrations varied between 1.5 and 6.5 Bq kg^-1 dw, Cs-137 was in the range 0.9-38.9 Bq kg^-1 dw, Pu-239(240) in the range 0.08-1.5 Bq kg^-1 dw and Pu-238 around 0.03 Bq kg^-1 dw. Special reference was also put on the comparison between the off-shore environment and data obtained from samples collected inside the Po river delta. in spite of the major accumulation of Cs-137 inside the estuarine environment, higher concentrations of strontium and plutonium isotopes were detected in the offshore environment.     

上海市公园绿地常见落叶树木叶片汞浓度时空特征及环境意义

植物叶片汞浓度与大气气态单质汞(GEM/Hg0)浓度的线性关系表明叶片汞浓度大小可用于指示植物生长区内GEM浓度的高低水平.通过分析上海市绿地公园(25座)中常见落叶树木樱花、水杉、法桐叶片汞浓度的时空变化特征,探究区域内GEM含量水平及分布特征.2017年5—10月对7座公园中这3种树木叶汞浓度进行连续监测,结果显示叶汞浓度与叶片生长时间呈显著线性正相关关系(P<0.01),表明叶片在生长期内不断吸收累积大气汞.而且在生长期内,3种树木叶汞浓度日累积速率(g·kg^-1·d^-1)具有相似的变化趋势,意味着不同树木叶汞的累积对外界环境的响应可能是一致的,除树种差异外.同年11月初,25座公园(包含上述7座)中樱花、水杉、法桐衰老叶片叶汞浓度为(54.2±12,31.8—76.7)μg·kg^-1、(42.0±9,23.5—67.9)μg·kg^-1、(36.1±11,21.4—60.3)μg·kg^-1(平均值,范围),有显著的种间差异(P<0.01),而在中心城区和郊区间无显著差异(P>0.05).空间插值分析结果初步表明衰老叶片叶汞浓度的空间梯度差异不大,且高值区域没有完全重合.这表明了利用衰老叶片叶汞浓度反映区域GEM浓度整体水平空间分布规律存在一定的不确定性,仍需进一步深入研究.     

The Influence of Varying Algal Biomass On Contaminant Exposure in Benthic-Planktonic Mesocosms: Copper (Ii)

A series of mesocosms was exposed to a suite of light treatments and nutrient enrichment in order to generate algal communities of varying biomass. the influence of this biomass on the speciation of copper (II) was studied. Distribution coefficients (_Kd,Lkg-1) were relatively high (log_Kd = 5 to 7), indicative of robust trace metal sequestration, and were likely controlled by the particulate organic carbon content (foc). Differences in _Kd over time and among treatments were significant, as was the relationship between _Kd and foc. Fluorescence quenching was used to determine binding capacities (_Lt, M) and their associated binding constants (_Kcond,M^-1) in order to model the solid phase copper speciation. the _Kcond ranged between 2.1 and 5.2 × 10¹²M^-1, indicating a very strong copper-ligand complex, and was higher in mesocosms that received more light. the light _Lt increased over time, dramatically after the nutrient enrichment, but did not vary systematically among light treatments. _Lt ranged from 7.2 × 10- 7 to 4.9 × 10- 5 M. the large magnitudes of _Kd, _Kcond and _Lt ensured that greater than 97% of total copper in the mesocosms was complexed by organic matter. the total copper concentration ([Cu]_T, M) needed to reach a target dissolved copper concentration of 10^-12.5 M (pCu = 12.5) was determined for each mesocosm over time. [Cu]_T was between 8.02 × 10^-5 and 3.41 × 10^-2 M, and increased over time. the [Cu]_T normalized to the target pCu (Effective Dose Ratio, EDR) increased directly with increases in algal biomass, indicating a direct link between system productivity and copper exposure. Approximately 45% of the variance in EDR was explained by variance in total biomass, while the residual variance in EDR was due likely to differences in the strengths of particle associations and magnitude of binding capacities.     

Competitive adsorption and desorption of copper and lead in some soil of North China

The competitive adsorption and desorption of Pb(II) and Cu(II) ions in the soil of three sites in North China were investigated using single and binary metal solutions with 0.01 mol·L^-1 CaCl₂ as background electrolyte. The desorption isotherms of Pb(II) and Cu(II) were similar to the adsorption isotherms, which can be fitted well by Freundlich equation (R₂>0.96). The soil in the three sites had greater sorption capacities for Pb(II) than Cu(II), which was affected strongly by the soil characteristics. In the binary metal solution containing 1∶1 molar ratio of Pb(II) and Cu(II), the total amount of Pb(II) and Cu(II) adsorption was affected by the simultaneous presence of the two metal ions, indicating the existence of adsorption competition between the two metal ions. Fourier transform infrared (FT-IR) spectroscopy was used to investigate the interaction between soil and metal ions, and the results revealed that the carboxyl and hydroxyl groups in the soil were the main binding sites of metal ions.     

Identification of cadmium-induced genes in maize seedlings by suppression subtractive hybridization

A maize variety, Huatian-1, had an unusually low translocation rate of cadmium (Cd) (59.6 mg·kg^-1 in the roots and 0.093 mg·kg^-1 in the grain) compared to 24 other varieties while being grown in soils with 16.50 mg·kg^-1 Cd. This indicates that this particular species may have special mechanisms that affect the absorption and translocation pattern of Cd. In this paper, the technique of suppression subtractive hybridization (SSH) was used to isolate and identify Cd-induced genes from Huatian-1 hydroponically ?exposed? to? 0.1 mM ?CdCl₂ ?for? 1 h,? 12 h, 24 h, and 48 h. We found a total of 15 differentially expressed genes in the four groups; 2, 3, 4, and 6 genes were from the groups of 1 h, 12 h, 24 h, and 48 h treatment, respectively. Phospholipase PLDb1 mRNA, adenosine triphosphate (ATP) phosphoribosyl transferase 2, and Sp17 were turned on in the maize in response to Cd stress, and it might provide new clues to explain the mechanism of maize tolerance to Cd.     

Effects of rape straw and red mud on extractability and bioavailability of cadmium in a calcareous soil

Screening of cost-effective soil amendments is important to develop “in situ” remediation techniques for cadmium (Cd) contaminated soils. In this study, different soil amendments, including red mud, a by-product of the alumina industry, and acid-treated, nano-treated by nano-particle milling, nano and acid-treated red muds, zeolite, corn straw, and rape straw, were evaluated to immobilize Cd in two added levels (2 and 5 mg Cd·kg^-1 soil) in a calcareous soil by single and sequential extractions and by cucumber (Cucumis sativus L.) pot experiments. Results indicated that cruciferous rape straw significantly decreased the concentrations of water soluble, extractable Cd in soils, and Cd in cucumber plants, and it was more effective than gramineous corn straw. Also, red mud generally decreased the extractability and bioavailability of Cd added to calcareous soils more effectively than zeolite. Furthermore, the efficiency of red mud could be increased by the treatment of nano-particle milling due to the increase in specific surface area of red mud. It is potential to use rape straw and red mud as soil amendments to develop a cost-effective and efficient “in situ” remediation technology for Cd mildly contaminated calcareous soils.     

Adsorption and desorption of steroid hormones on saline soil

● Organic matter content significantly affected adsorption of E2/EE2 on saline soil. ● EE2 possessed higher competition intensity for adsorption sites than E2. ● The adsorption of E2/EE2 on saline soil was a spontaneous exothermic process. ● Desorption capacity of EE2/E2 accounted for 40%/78% of the total adsorption capacity. Soil organic matter content was the main driving factor affecting adsorption and desorption process of 17β-estradiol (E2) and 17α-ethynylestradiol (EE2) on saline soil. The adsorption and desorption of E2 and EE2 on three saline soils showed the similar behavior that soil with the highest organic content possessed the highest adsorption capacity and the lowest desorption capacity for E2 and EE2. The adsorption capacity of untreated soil samples (with organic matter) was larger than that of soil samples without organic matter. For soil with the largest adsorption capacity, adsorption capacity of E2/EE2 on the untreated soil and soil colloid (with organic matter) respectively reached 0.15/0.30 μg/g and 0.16/0.33 μg/g while the soil and soil colloid without organic matter hardly adsorbed pollutants. The adsorption capacity of E2/EE2 at the initial concentration of 100 μg/L was 25/15 times higher than that at the initial concentration of 5 μg/L. E2 and EE2 had the same adsorption sites on saline soil while EE2 possessed higher competition intensity for adsorption sites than E2. Pseudo-first-order model (R² = 0.995–0.986) and Langmuir model (R² = 0.989–0.999) could better fit the adsorption process of E2 or EE2. The thermodynamic study further showed that the adsorption of E2/EE2 on saline soil was a spontaneous exothermic process. The desorption capacity of EE2/E2 accounted for 40%/78% of the total adsorption capacity to possibly exert potential risk to the groundwater. The variation of the salinity led to the variation of soil organic carbon which subsequently changed the adsorption and desorption behaviors of endocrine disrupting chemicals in coastal saline soil. This study provides a new insight on the interfacial behavior of endocrine disrupting chemicals on saline soil.     

Effects of organic acids on Cd adsorption and desorption by two anthropic soils

The objective of this experiment was to study the effects of malic, tartaric, oxalic, and citric acid on the adsorption and desorption characteristics of Cd by two typical anthropic soils (lou soil and irrigation-silted soil) in North-west China. Cadmium adsorption and desorption were studied under a range of temperatures (25°C, 30°C, 35°C, 40°C), organic acid concentrations (0.5–5.0 mmol·L^-1), and pH values (2–8). The results showed that the Cd adsorption capacity of the lou soil was significantly greater than that of the irrigation-silted soil. Generally, Cd adsorption increased as the temperature increased. In the presence of NaNO₃, the adsorption of Cd was endothermic with ΔH values of 31.365 kJ·mol^-1 for lou soil and 28.278?kJ·mol^-1 for irrigation-silted soil. The endothermic reaction indicated that H bonds were the main driving force for Cd adsorption in both soils. However, different concentrations of organic acids showed various influences on the two soils. In the presence of citric acid, chemical adsorption and van der Waals interactions were the main driving forces for Cd adsorption rather than H bonds. Although the types of organic acids and soil properties were different, the effects of the organic acids on the adsorption and desorption of Cd were similar in the two soils. The adsorption percentage of Cd generally decreased as organic acid concentrations increased. In contrast, the adsorption percentage increased as the pH of the initial solution increased. The exception was that adsorption percentage of Cd increased slightly as oxalic acid concentrations increased. In contrast, the desorption percentage of Cd increased with increasing concentrations of organic acids but decreased as the initial solution pH increased.